Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T152/00—Resilient tires and wheels
  • Y10T152/10—Tires, resilient
  • Y10T152/10495—Pneumatic tire or inner tube
  • Y10T152/10765—Characterized by belt or breaker structure

Definitions

• the present invention relates to rubber compositions intended in particular for the manufacture of a protective elastomeric layer having an improved air impermeability, which can be used in particular for the manufacture of tires.
• a tire with a radial carcass reinforcement in known manner, comprises a crown topped with a tread, two beads intended to be in contact with a mounting rim, two sidewalls connecting the beads to the top.
• the crown comprises a belt circumferentially reinforcing the tire and arranged radially between the carcass reinforcement and the tread.
• This belt consists of several layers (or "layers") of rubber reinforced or not by reinforcements such as cables or mono filaments, metal or textile type.
• One of the concerns of the tire manufacturers is to increase the service life and in particular to improve the endurance, vis-à-vis oxidizing processes, rubber compositions, metal or textile reinforcements and the interfaces between these mixtures and these reinforcements.
• One of the solutions consists in arranging a protective elastomer layer next to the components of the tire to be protected.
• the protection can be increased by increasing the thickness of this protective elastomer layer.
• Such an increase in mass leads to an increase in the cost price of the tire, and a rise in rolling heating of the mixtures that are used inside the tire.
• Other solutions propose to fix the oxygen in the protective elastomeric layer by decreasing the level of antioxidant, but this does not allow an improvement in the service life of the carcass reinforcement.
• compositions based on a diene elastomer, a crosslinking system, a reinforcing filler, and comprising at least one metal salt, a lamellar filler, which makes it possible to overcome all the disadvantages of the various solutions mentioned above.
• This composition has in fact as good processability and mechanical properties as the compositions of the prior art, as well as improved properties of impermeability to oxygen over a wide temperature range, from ambient temperatures when the tire is stopping until temperatures of the tire in operation.
• a first subject of the invention relates to a rubber composition based on at least one diene elastomer, a reinforcing filler and a vulcanization system characterized in that it comprises at least:
• the tires of the invention are particularly intended for equipping tourism-type motor vehicles, SUVs ("Sport Utility Vehicles"), two wheels (in particular motorcycles), planes, such as industrial vehicles chosen from light trucks, "heavy vehicles”. - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles -, other transport or handling vehicles.
• the invention relates to the above tires both in the green (i.e., before firing) and the fired (i.e., after crosslinking or vulcanization) state.
• the invention also relates to the use as an oxygen barrier layer, in a rubber article, of an elastomeric composition whose formulation is as defined above.
• the invention as well as its advantages will be readily understood in the light of the description and the following exemplary embodiments, as well as FIGS. 1 and 2 relating to these examples, which schematize, in radial section, two examples of radial tires in accordance with FIG. 'invention.
• the rubber compositions are characterized, before and after firing, as indicated below.
• the Mooney plasticity measurement is carried out according to the following principle: the composition in the green state (ie, before firing) is molded in a cylindrical enclosure heated to 100 ° C.
• T 1 is the induction time, that is to say the time required for the beginning of the vulcanization reaction.
• the permeability values are measured using a MOCON OXTRAN 2/60 permeability tester at 40 ° C. and 80 ° C. Samples baked in the form of discs of a determined thickness (approximately 0.8 to 1 mm) are mounted on the apparatus and sealed with vacuum grease. One side of the disc is kept under 10 psi (about 0.7 bar) of nitrogen while the other side is kept under 10 psi of oxygen. The increase in oxygen concentration is monitored by using a "Coulox" oxygen sensor on the face maintained under nitrogen. The oxygen concentration is noted on the face maintained under nitrogen to reach a constant value, used to determine the permeability to oxygen.
• the rubber composition according to the invention is based on at least one diene elastomer, a reinforcing filler and a crosslinking system characterized in that it comprises at least:
• the abbreviation "pce” means part by weight per 100 parts by weight of the elastomer or all of the elastomers present in the composition.
• composition-based is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another, less in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range of values from a to b (i.e., including the strict limits a and b).
• elastomer or “diene” rubber it is to be understood in a known way (one or more elastomers), at least in part (ie, a homopolymer or a copolymer) of diene monomers (monomers bearing two carbon-to-carbon double bonds). , conjugated or not).
• diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
• the term “essentially unsaturated” is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%);
• diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "substantially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
• the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
• iene elastomer can be understood more particularly to be used in the compositions according to the invention:
• diene elastomer any type of diene elastomer
• the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
• conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as for example 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• alkyl-1,3-butadienes such as for example 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexa
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, viny lnaphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
• the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
• the elastomers can be for example block, statistical, sequence, microsequential, and be prepared in dispersion or in solution; they can be coupled and / or star or functionalized with a coupling agent and / or starring or functionalization.
• alkoxysilane groups such as as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445) or groups polyethers (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).
• functionalized elastomers mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
• Tg glass transition temperature
• styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol%) in -1,2 bonds of the butadiene part of between 4% and 75%, a content ( mol%) in trans-1,4 bonds of between 10% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a Tg of -40 ° C. to - 80 0 C, isoprene-styrene copolymers and especially those having a styrene content of between 5% and 50% by weight and a Tg comp between - 25 ° C and - 50 ° C.
• butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly between 10% and 40%, an isoprene content between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (mol%) in units - 1,2 of the butadiene part of between 4% and 85%, a content (mol%) in trans-1,4 units of the butadiene part of between 6% and 80%, a content (mol%) in units -1 , 2 plus -3,4 of the isoprenic part of between 5% and 70% and a content (mol%) in trans units -1,4 of the isoprene part of between 10% and 50%, and more generally any butadiene copolymer -styrene-isoprene having a Tg between -
• the diene elastomer of the composition in accordance with the invention is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• BR polybutadienes
• IR synthetic polyisoprenes
• NR natural rubber
• butadiene copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
• SBIR butadiene-styrene
• the diene elastomer is predominantly (ie, for more than 50 phr) an SBR, whether it is an emulsion-prepared SBR ("ESBR") or an SBR prepared in solution (“SSBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), BR / NR (or BR / IR), or SBR / BR / NR (or SBR / BR / IR).
• SBR emulsion-prepared SBR
• SSBR SBR prepared in solution
• an SBR elastomer In the case of an SBR elastomer (ESBR or SSBR), an SBR having an average styrene content, for example between 20% and 35% by weight, or a high styrene content, for example 35 to 35% by weight, is used in particular. 45%, a vinyl content of the butadiene part of between 15% and 70%, a content (mol%) of trans-1,4 bonds of between 15% and 75% and a Tg of between -10 ° C. and - 55 ° C; such an SBR can be advantageously used in admixture with a BR preferably having more than 90% (mol%) of cis-1,4 bonds.
• the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer.
• isoprene elastomer in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer selected from the group consisting of natural rubber (NR) which can be plasticized or peptized, the polyisoprenes of synthesis (IR), the various isoprene copolymers and the mixtures of these elastomers.
• NR natural rubber
• IR polyisoprenes of synthesis
• isoprene copolymers examples include isobutene isoprene (butyl rubber - HR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
• This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
• compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
• the secondary rubber composition according to the invention has a diene elastomer having a glass transition temperature (Tg) greater than -35 ° C., hereinafter referred to as elastomer.
• Tg glass transition temperature
• elastomer glass transition temperature
• the rubber composition comprises between 0 and 80 phr, in particular between 30 and 70 phr, of "high Tg" elastomer.
• the "High Tg" elastomer is a styrene-butadiene copolymer (SBR).
• SBR styrene-butadiene copolymer
• a high Tg SBR with a styrene content of between 5% and 50% by weight and more particularly between 20% and 50%, a 1,2-butadiene content of the butadiene part of between 4% and 65% is used.
• the person skilled in the art knows how to modify the microstructure of an SBR elastomer to adjust its Tg.
• the high SBR Tg has a Tg preferably between -35 ° C. and 0 ° C., in particular greater than -30 ° C., and more preferably between -30 ° C. and -50 ° C. .
• SBR high Tg is, for example SBR Tg of -25 ° C, which comprises 24% of vinyl 1,2, 41% of styrene, 50% butadiene trans-1,4, 26% butadiene cis-1, 4.
• the "high Tg” elastomer is an epoxidized natural rubber (abbreviated "ENR").
• Epoxidized natural rubbers are used for their properties of excellent abrasion resistance, fatigue strength, flexural strength, and known to be particularly used in tire flanks. They can be obtained by epoxidation of natural rubber, for example by chlorohydrin or bromohydrin-based processes or processes based on hydrogen peroxides, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid).
• the epoxidation rate of the epoxidized natural rubber is preferably at least 3% (mol%), more preferably at least 5%, for example in a range of 10 to 40%.
• the epoxidation rate is less than 3%, the intended technical effect (improvement of the oxygen barrier effect) may be insufficient.
• the epoxidation rate is preferably at most 60%, more preferably at most 50%; when the epoxidation rate exceeds 60%, the molecular weight of the polymer decreases sharply.
• the invention relates to a rubber composition which comprises at least 0.01 to 0.3 phr of a metal salt.
• This metal salt is preferably selected from the first series, the second series or the third series of transition metals of the periodic table, or from the lanthanides.
• the metals may be for example manganese II or III, iron II or III, cobalt II or III, copper I or II, rhodium II, III, IV and ruthenium.
• the oxidation state of the metal when it is introduced is not necessarily that of the cationic active form.
• the metal is preferably manganese, nickel or copper, more preferably cobalt and even more preferably iron.
• the counterion for the metal includes especially chloride, acetate, stearate, palmitate, 2-ethylhexanoate, neodecanoate or naphthenate.
• iron (III) salts of fatty acids As iron (III) salts of fatty acids according to the invention, mention may be made of fatty acid salts: tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, henicosanoic, docosanoic and tricosanoic .
• the iron (III) salt is iron (III) acetylacetonate or iron (III) stearate.
• the lanthanide is selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, erbium, and the mixture of these rare earths, and more preferably cerium (IV) sulphate.
• Sulphide and molybdenum (IV) oxide are also particularly suitable.
• any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tires for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica, or a cutting of these two types of filler, including a cut of carbon black and silica.
• Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
• the reinforcing carbon blacks of the 100, 200 or 300 series for example the N234, N326, N330 blacks, or the higher series blacks (for example N660, N683, N772).
• the carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600).
• organic fillers other than carbon blacks mention may be made of the organic functionalized polyvinylaromatic fillers as described in the applications WO-A-2006/069792 and WO-A-2006/069793, or else the organic fillers of polyvinyl non-aromatic functionalized as described in applications WO-A-2008/003434 and WO-A-2008/003435.
• any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or “non-blackfiller” as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words apt to replace, in its reinforcing function, a conventional carbon black of pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• reinforcing inorganic filler is present indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• reinforcing inorganic filler also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• Suitable reinforcing inorganic fillers are mineral fillers of the siliceous type, in particular silica (SiO 2), or of the aluminous type, in particular alumina (Al 2 O 3).
• the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa the Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia
• the Hi-SiI silica EZ150G from the PPG company
• the Zeopol 8715, 8745 and 8755 silicas of the Huber Company the high surface area silicas as described in the application WO 03/16837.
• the content of total reinforcing filler is between 10 and 200 phr, more preferably between 20 and 150 phr, the optimum being in a known manner different according to particular applications targeted: the level of reinforcement expected on a bicycle tire, for example, is of course less than that required on a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for commercial vehicles such as heavy goods vehicles.
• the rubber composition comprises carbon black and silica.
• the carbon black content is preferably in a range from 5 to 90 phr, more preferably from 10 to 60 phr
• the silica content is preferably between 5 and 90 phr, more preferably between 10 and 60 phr. pc.
• a reinforcing filler comprising between 30 and 150 phr, more preferably between 50 and 120 phr of inorganic filler, particularly of silica, and optionally carbon black; the carbon black, when present, is preferably used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).
• an at least bifunctional coupling agent is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
• polysulfide silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).
• x is an integer of 2 to 8 (preferably 2 to 5);
• - A is a divalent hydrocarbon radical (preferably alkylene groups C 1 -C 18 or arylene groups C 2 -C 6, particularly alkylene Ci-Cio, in particular C 1 -C 4, particularly the propylene);
• radicals R 1 substituted or unsubstituted, identical or different, represent an alkyl group C 1 -C 18 alkyl, C5-C 1 8 or C 6 cis (preferably alkyl groups -C 6 , cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
• radicals R 2 substituted or unsubstituted, identical or different, represent an alkoxy group of C 1 -C 18 cycloalkoxy or C5-C 1 8 (preferably a group selected from Ci-Cs alkoxyl and cycloalkoxyls Cs-Cs, more preferably still a group selected from C 1 -C 4 alkoxyls, in particular methoxyl and ethoxyl).
• polysulphurized silanes By way of examples of polysulphurized silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy) -alkyl (C 1 -C 4 ) -alkyl (C 1 -C 4 ) -alkyl (especially disulfide, trisulphide or tetrasulfide) polysulphides. ), such as polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
• TESPT bis (3-triethoxysilylpropyl) tetrasulfide
• TESPD bis (3-triethoxysilylpropyl) tetrasulfide
• POS polyorganosiloxanes
• the content of coupling agent is preferably between 2 and 20 phr, more preferably between 4 and 12 phr.
• the composition according to the invention has the essential characteristic of comprising from 10 to 150 phr of a lamellar filler.
• This charge can be either an inert filler or a reinforcing or semi-reinforcing filler, any filler capable of reducing the gas permeability characteristics through a protective elastomeric element, from the composition.
• the so-called lamellar charges (in English "platy fi llers”) are well known to those skilled in the art. They have been used in particular in pneumatic tires to reduce the permeability of conventional gas-tight layers ("inner-liners”) based on butyl rubber. In these butyl-based layers, they are generally used at relatively low levels, usually not exceeding 10 to 25 phr (see, for example, US Patent Specification 2004/0194863, WO 2006/047509).
• They are generally in the form of plates, platelets, sheets or stacked sheets, with a more or less marked anisometry of these particles.
• this aspect ratio is between 1 and 1000, in particular between 1 and 500.
• lamellar fillers are preferably of micro-metric size, that is to say that they are in the form of microparticles whose median size or length (L) is greater than 0.05 ⁇ m.
• the median length (L) of the particles is between 0.05 and 500 ⁇ m, more preferably between 0.2 and 250 ⁇ m.
• the median thickness (E) of the particles is for its part between 10 and 500 nm, preferably between 50 and 250 nm.
• the lamellar filler is present in the composition according to the invention in levels ranging from 10 phr to 150 phr, in particular from 20 to 100 phr, preferably from 15 to 80 phr, and even more preferably from 15 to 50 phr. .
• the lamellar fillers used in accordance with the invention are chosen from the group consisting of graphites, phyllosilicates and mixtures of such fillers.
• phyllosilicates there may be mentioned clays, talcs, micas, kaolins, these phyllosilicates may or may not be modified for example by a surface treatment; examples of such modified phyllosilicates include micas coated with titanium oxide, clays modified with surfactants ("organo clays").
• Lamellar fillers with a low surface energy are preferably used, such as those chosen from the group consisting of graphites, talcs, micas and mixtures of such fillers, the latter being able to be modified or not, more preferably still in the group consisting of graphites, talcs and mixtures of such fillers.
• the graphites can be used natural graphites such as synthetic graphites.
• compositions of the invention may contain a single graphite or a mixture of several graphites.
• talcs As an example of talcs, mention may be made of talcs marketed by Luzenac.
• micas examples include micas marketed by CMMP ("Mica-MU®”, “Mica-Soft®”, “Briomica®” for example), vermiculites (especially Shawatec® vermiculite sold by CMMP or "Microlite®” vermiculite marketed by WR Grace), modified or treated micas (for example, the “Iriodin®” range marketed by Merck).
• non-reinforcing fillers are used as lamellar fillers, and more particularly the silicon-based lamellar mineral fillers are suitable.
• lamellar inorganic fillers based on silicon are suitable phyllosilicates and particularly those included in the group consisting of smectites, kaolin, talc, mica, vermiculite and montmorillonites.
• the organic structure with which the inert filler is associated is a surfactant of formula: - M + R 1 R 2 R 3 -, where M represents a nitrogen, sulfur, phosphorus or pyridine and wherein R 1 , R 2 , and R 3 represents a hydrogen atom, an alkyl group, an aryl group or an allyl group, R 1 , R 2 , and R 3 being identical or different.
• the phy Ho silicates of montmorillonite organo-modified type are suitable for the invention.
• montmorillonites modified with a surfactant such as a dioctadecyldimethyl dihydrogenated quaternary ammonium salt.
• Such organo-modified montmorillonite is marketed in particular by the company Southern Clay Products under the trade name: "CLOISITE 2OA", of density 2.6 and whose particle diameter is between 0.2 and 0.5 microns.
• surfactants based on quaternary ammonium salts can be further used to modify phy Ho silicates as described in patent application WO 2006/047509.
• the lamellar fillers are kaolin particles previously described, commercially available, and sold by Imerys under the name "Kerbrient SP20”.
• the introduction of the lamellar fillers into the elastomeric composition can be carried out according to various known methods, for example by mixing in solution, by mass mixing in an internal mixer, or by extrusion mixing.
• the operation consists in sieving a defined quantity of sample (for example 200 g) on a vibrating table for 30 min with different sieve diameters (for example, according to a reason for progression, with meshes of 75, 105, 150 , 180, etc.); the refusals collected on each sieve are weighed on a precision scale; we deduce the% of refusal for each mesh diameter with respect to the total weight of product; the median size (or median diameter) is finally calculated in a known manner from the histogram of the particle size distribution.
• a defined quantity of sample for example 200 g
• different sieve diameters for example, according to a reason for progression, with meshes of 75, 105, 150 , 180, etc.
• the refusals collected on each sieve are weighed on a precision scale; we deduce the% of refusal for each mesh diameter with respect to the total weight of product; the median size (or median diameter) is finally calculated in a known manner from the histogram of the particle size distribution.
• the rubber compositions according to the invention also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example pigments, protective agents such as anti-ozone waxes, chemical ozonants, antioxidants, plasticizers, anti-fatigue agents, reinforcing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M), a crosslinking system based on either sulfur, or sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators, vulcanization activators.
• the rubber compositions of the invention preferentially use a high temperature glass transition plasticizing resin (Tg), whose Tg is greater than 20 ° C.
• plasticizing resin is reserved in this application, by definition, to a compound which is solid on the one hand at room temperature (23 ° C.) (as opposed to a plasticizer compound).
• liquid such as an oil
• on the other hand compatible that is to say miscible with the rate used
• the level of plasticizing hydrocarbon resin is preferably in a range from 1 to 20 phr. Below the minimum indicated, the intended technical effect may prove to be insufficient, whereas beyond 20 phr it is exposed to an increase in the tackiness of the compositions in the green state, on the mixing tools, which can in some cases become prohibitive from an industrial point of view.
• the plasticizing hydrocarbon resin has at least one, more preferably all, of the following characteristics: a number-average molecular weight (Mn) of between 400 and 2000 g / mol;
• Ip Mw / Mn with Mw weight average molecular weight
• the glass transition temperature Tg is measured in a known manner by DSC (Differential Scanning Calorimetry), according to ASTM D3418 (1999), and the softening point ("softening point”) is measured according to the ASTM E-28 standard.
• the macrostructure (Mw, Mn and Ip) of the hydrocarbon plasticizing resin is determined by steric exclusion chromatography (SEC): solvent tetrahydrofuran; temperature 35 ° C; concentration 1 g / 1; flow rate 1 ml / min; filtered solution on 0.45 ⁇ m porosity filter before injection; Moore calibration with polystyrene standards; set of 3 "WATERS” columns in series (“STYRAGEL” HR4E, HR1 and HR0.5); differential refractometer detection (“WATERS 2410") and its associated operating software (“WATERS EMPOWER”).
• SEC steric exclusion chromatography
• the above resins can be aliphatic, naphthenic, aromatic or aliphatic / aromatic type that is to say based on aliphatic and / or aromatic monomers. They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins). They are preferentially exclusively hydrocarbons, that is to say that they contain only carbon and hydrogen atoms.
• the plasticizing hydrocarbon resin is chosen from the group consisting of homopolymer or copolymer resins of cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD), terpene homopolymer or copolymer resins, C5 homopolymer or copolymer resins, and mixtures of these resins.
• CPD cyclopentadiene
• DCPD dicyclopentadiene
• terpene homopolymer or copolymer resins C5 homopolymer or copolymer resins, and mixtures of these resins.
• hydrocarbon plasticizing resins mention may be made in particular of the resins of homo- or copolymers of alphapinene, betapinene, dipentene or polylimonene, C5-cut, for example of C5-cut copolymer / styrene or of C5-cut / C9-cut copolymer, can be used alone or in combination with plasticizing oils, for example MES or TDAE oils.
• plasticizing oils for example MES or TDAE oils.
• compositions may also contain, in addition to the coupling agents, coupling activators, inorganic charge-covering agents or, more generally, processing aids that can be used in a known manner, thanks to an improvement in the dispersion. of the charge in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
• hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
• compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called “non-productive” phase) at high temperature, up to a maximum of maximum temperature between 110 0 C and 190 0 C, preferably between 130 0 C and 180 0 C, followed by a second phase of mechanical work (so-called “productive” phase) to a lower temperature, typically less than 110 0 C, for example between 40 0 C and 100 0 C, finishing phase during which is incorporated the crosslinking system.
• a first phase of work or thermomechanical mixing at high temperature, up to a maximum of maximum temperature between 110 0 C and 190 0 C, preferably between 130 0 C and 180 0 C
• a second phase of mechanical work so-called “productive” phase
• the method according to the invention for preparing a rubber composition comprises the following steps: incorporating in a diene elastomer, during a first step (called “non-productive"), at least one reinforcing filler, a lamellar filler and a metal salt, by thermomechanically kneading the whole (for example in one or several times), until a maximum temperature of between 0 ° C. and 190 ° C. is reached; cool the assembly to a temperature below 100 0 C; then incorporate, during a second step (called “productive"), a crosslinking system; knead everything to a maximum temperature below 110 ° C.
• the non-productive phase is carried out in a single thermomechanical step in the course of which, in a suitable mixer such as a conventional internal mixer, all the necessary basic constituents (the diene elastomer, the reinforcing filler, from 10 to 150 phr of the lamellar filler and from 0.01 to 0.3 phr of metal salt), then in a second stage, for example after one to two minutes of mixing, the other additives any additional charge recovery or processing agents, with the exception of the crosslinking system.
• the total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
• the mixture thus obtained After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 0 C and 100 0 C), the crosslinking system. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• an external mixer such as a roll mill, maintained at low temperature (for example between 40 0 C and 100 0 C), the crosslinking system.
• the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• the actual crosslinking system is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator.
• a primary vulcanization accelerator in particular a sulfenamide type accelerator.
• various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc.
• the sulfur content is preferably between 0.5 and 10 phr, more preferably between 1.5 and 8, that of the primary accelerator is preferably between 0.5 and 5.0 phr.
• accelerator any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, especially thiazole type accelerators and their derivatives, thiuram type accelerators, zinc dithiocarbamates.
• accelerators are more preferably selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazylsulfenamide (abbreviated “TBBS”), N-tert-butyl-2-benzothiazylsulfenimide (abbreviated “TBSI”), zinc dibenzyldithiocarbamate (in abbreviated “ZBEC”) and mixtures of these compounds.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohex
• a primary accelerator of the sulfenamide type is used.
• the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate especially for a characterization in the laboratory, or extruded, for example to form a rubber profile intended to be used as an elastomeric layer protection of a tire.
• Axial a direction parallel to the axis of rotation of the tire; this direction can be oriented “axially inward” when it is directed towards the inner cavity of the tire and “axially outward” when it is directed towards the outside of the tire;
• Ring plane plane containing the axis of rotation of the tire
• Ring direction means a direction intersecting the axis of rotation of the tire and perpendicular thereto; this direction can be oriented “radially inward” or “radially outward” as it moves towards the axis of rotation of the tire or out of said axis; - “reinforcement” or “reinforcing element”, both monofilaments and multifilaments, or assemblies such as cables, twisted or even any type of equivalent assembly, and this, whatever the material and the treatment of these reinforcements, for example surface treatment or coating such as scrubbing, or pre-gluing to promote adhesion to the rubber; - "radially oriented reinforcement” or “radial reinforcement”, a reinforcement contained substantially in the same radial plane or in a plane forming with a radial plane an angle less than or equal to 10 degrees.
• the rubber composition described above can be used in the tire as a protective layer in at least a portion of the tire.
• layer rubber protection means any three-dimensional element, rubber composition (or “elastomer”, both considered synonymous), of any shape and thickness, including sheet, strip, or other element of any straight section, for example rectangular or triangular.
• the protective elastomer layer may be used as a sub-layer disposed in the crown of the tire, on the one hand between the tread, ie, the portion intended to come into contact with the road during driving, and on the other hand the belt reinforcing said vertex.
• the thickness of this protective elastomeric layer is preferably in a range from 0.5 to 10 mm, especially in a range of 1 to 3 mm.
• the composition according to the invention can be used to form a protective elastomeric layer, annular, disposed in the region of the shoulder of the tire, radially between the carcass reinforcement and the crown frame.
• Another preferred embodiment of the invention may be the use of the composition according to the invention to form a protective elastomer layer disposed against the carcass ply.
• Figures 1 and 2 appended represent in radial section, very schematically (particularly without respecting a specific scale), two preferred examples of radial carcass reinforcement tires, according to the invention.
• the schematized tire 1 comprises a crown 2 surmounted by a tread 3, two inextensible beads 4 in which is anchored a carcass reinforcement 6.
• the crown 2, joined to said beads 4 by two flanks 5, is in a manner known per se reinforced by a crown reinforcement or "belt" 7 at least partly metallic and radially external with respect to the carcass reinforcement 6, constituted by two superposed plies, each of these plies being reinforced by metal cables parallel to each other in each layer and crossed from one sheet to another.
• the carcass reinforcement 6 is here anchored in each bead 4 by winding around a bead wire 4a, 4b, to form in each bead a turnaround 6a, 6b.
• the tire 1 is here shown mounted on its rim 9.
• the carcass reinforcement 6 consists of at least one ply reinforced by radial textile cables, that is to say that these cables are arranged substantially parallel to each other. other and extend from one bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is situated midway between the two beads 4 and passes through the middle of the crown frame 7.
• this tire 1 also comprises, in known manner, an inner liner layer 10 (commonly called “inner liner” or “inner liner”) which defines the radially inner face of the tire and which is intended to protect the carcass ply from the air diffusion from the inner cavity to the tire.
• an inner liner layer 10 commonly called “inner liner” or “inner liner”
• FIG. 1 illustrates a possible embodiment of the invention, according to which the protective elastomer layer 8, and disposed below the tread (ie, radially inwardly from the tread) and above the belt (ie, radially outwardly from the latter), in other words between the tread 3 and the belt 7.
• At least one annular protective elastomeric layer 8a, 8b is disposed in the region of the shoulder 11 of the tire, radially between the carcass reinforcement 6 and the outer parts of the crown frame 7.
• a protective elastomer layer may be disposed against the carcass reinforcement 6, in particular between the inner liner 10 and the carcass reinforcement 6, or possibly in the zone outside the carcass reinforcement 6.
• the protective elastomeric layer is preferably disposed in at least one zone of the tire located:
• this protective elastomer layer gives the tires of the invention an effective protection against the spurious effects of oxygen in the air that can penetrate through their tread and their sidewalls. , and spread to their belt and carcass ply, as demonstrated in the following rubber testing.
• compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded in the form of a layer to make tires. .
• Example 1 Rubber compositions with a lamellar filler and a metal salt
• This test is intended to show the improvement in oxygen impermeability performance of three compositions of a tire protection elastomer layer according to the invention, compared to a control composition.
• compositions comprise a natural rubber, iron acetylacetonate.
• the compositions according to the invention further comprise a platy filler; either graphite whose particle diameter is of the order of 20 microns (composition C 1.2), or graphite whose particle diameter is about 3 microns (composition Cl.3), or kaolin (composition C 1.4), and a high hydrocarbon plasticizing resin Tg for compositions C1.2 and C1.3.
• compositions according to the invention with or without plasticizing resin have, in the green state, a better processability (lower Mooney viscosity) than the control composition C 1.1.
• compositions C 1.2 to C 1.4 are not significantly modified with respect to the control composition Cl. After firing, it can be seen that the MA10 modules of compositions C 1.2, C 1.3 and C 1.4 according to the invention are globally equivalent to those of control composition C 1.1.
• compositions C 1.2, C 1.3 and C 1.4 in accordance with the invention comprising a metal salt and as lamellar filler respectively graphite and kaolin, have a permeability much lower than that of the control composition C 1.1.
• this decrease in the permeability of the mixtures is more marked for the compositions C 1.2 and C 1.3, which additionally comprise a high-level hydrocarbon plasticizing resin Tg.
• Example 2 Rubber compositions with a lamellar filler, a metal salt and a so-called "high Tg” elastomer
• This test is intended to show the improvement in oxygen impermeability performance of three compositions of a tire protection elastomer layer according to the invention, compared to a control composition.
• compositions in accordance with the invention additionally comprise, with respect to compositions C 1.2 to C 1.4, a diene elastomer called "high Tg", which is a styrene-butadiene copolymer for compositions C2.3 to C2.6, and a rubber epoxidised natural for the composition C2.2.
• compositions according to the invention have in the green state a better processability (Mooney lower) than the control composition C2.1.
• compositions C2.4 to C2.6 are not significantly impacted with respect to control composition C2.1.
• the rheological properties of compositions C2.2 and C2.3 allow their use in pneumatics.
• compositions C2.2 to C2.6 according to the invention comprising a metal salt, a lamellar filler and a high Tg elastomer, have a permeability much lower than that of the control composition C2.1 and the compositions C 1.2 to C 1.4.
• this decrease in the permeability of the compositions is more marked for compositions C2.2 and C2.3 which comprise a montmorillonite-type lamellar filler.
• Acetylacetonate iron Fe (Acac) 3 from the company CPAS;
• Epoxidized natural rubber "ENR-25" (Guthrie Polymer Company);
• Acetylacetonate iron Fe (Acac) 3 from the company CPAS;

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